CN101903435B - Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing z-1,1,1,4,4,4-hexafluoro-2-butene and their uses in the preparation of polyisocyanate-based foams - Google Patents
Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing z-1,1,1,4,4,4-hexafluoro-2-butene and their uses in the preparation of polyisocyanate-based foams Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing cis-1,1,1,4,4,4-hexafluoro-2-butene are disclosed. The foam-forming composition contains (a) an azeotropic or azeotrope-like mixture of cis-1,1,1,4,4,4-hexafluoro-2-butene with methyl formate, 1,1,1,3,3-pentafluorobutane, trans-1,2-dichloroethylene, pentane, isopentane, cyclopentane, HFC-245fa, or dimethoxymethane; and (b) an active hydrogen-containing compound having two or more active hydrogens. Also disclosed is a closed-cell polyurethane or polyisocyanurate polymer foam prepared from reaction of an effective amount of the foam-forming composition with a suitable polyisocyanate. Also disclosed is a process for producing a closed-cell polyurethane or polyisocyanurate polymer foam by reacting an effective amount of the foam-forming composition with a suitable polyisocyanate.
Description
Present patent application requires the right of priority of the U.S. Patent application 61/015214,61/015218 and 61/015221 of the U.S. Patent application submission on December 20th, 61/015061,61/015027,61/015086,61/015089 and 61/015092,2007 of submitting on December 19th, 2007.
Invention field
Disclosure relates to formation of foam composition herein, described formation of foam composition comprises (a) containing cis-1,1,1, the azeotropic of 4,4,4-hexafluoro-2-butylene or Azeotrope-like mixtures, (b) containing the compound of active hydrogen, and prepare urethane and polyisocyanurate foam with this composition.
Background technology
Closed-cell foam based on polyisocyanates is widely used in insulation applications, for example, for Architectural Construction and for the manufacture of energy-saving electric equipment.In building industry, urethane/poly-isocyanurate stock board is because its heat-proof quality and supporting capacity are used as roof Material and wallboard material.Mould waters with spray urethane foam and is widely used in multiple application, comprise make thermal insulation of roof, make main equipment such as storage tank heat insulation, make equipment heat insulation such as reezer system and refrigerator, make refrigerator car and railcar heat insulation etc.
The manufacture of all these various types of urethane/polyisocyanurate foams needs whipping agent to carry out.Heat insulation foam depends on use halohydrocarbon foaming agent, to not only can make polymer foaming, and is mainly because they have low steam heat conductance-very important insulation value feature.In the past, polyurethane foam is used CFC (Chlorofluorocarbons (CFCs), for example CFC-11, trichlorofluoromethane) and HCFC (Hydrochlorofluorocarbons, for example HCFC-141b, the chloro-1-fluoroethane of 1,1-bis-) as main whipping agent.But owing to relating to chloride molecule such as CFC and HCFC in stratospheric ozone destroys, therefore the production of CFC and HCFC and use have been subject to the restriction of Montreal Protocol.Recently, the hydrogen fluorohydrocarbon (HFC) that does not cause stratospheric ozone to destroy has been used as the whipping agent of polyurethane foam.HFC example for this application is HFC-245fa (1,1,1,3,3-pentafluoropropane).HFC does not have destructiveness to stratospheric ozone, but receives publicity because they promote " Greenhouse effect ", that is, they promote Global warming.Because they can promote Global warming, therefore HFC has been subject to sifting, and their widespread use also can be restricted in the future.
Propose that hydrocarbon is as foam foaming agent.But these compounds are inflammable, and many be photochemically reactive, therefore impel produce ground level ozone (, smog).This compounds is commonly called volatile organic compounds (VOC) and is subject to the restriction of ENVIRONMENTAL LAW.
Need to prepare by the essentially no ozone depletion potentiality of use (ODP) and the whipping agent that do not there is global warming up trend (GWP) or there is low-down global warming up trend (GWP) foam that low combustible, well insulated and high dimensional stability are provided.Cis-1,1,1,4,4,4-hexafluoro-2-butene (Z-FC-1336mzz or Z-CF
3cH=CHCF
3) be a kind of material standed for preferably.
Japanese Patent 05179043 discloses and has attempted to use the whipping agent of cis-1,1,1,4,4,4-hexafluoro-2-butene as polyurethane foam.
Summary of the invention
Present patent application comprises eight kinds of dissimilar formation of foam compositions, the azeotropic that each composition comprises cis-1,1,1,4,4,4-hexafluoro-2-butene or Azeotrope-like mixtures.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) azeotropic of cis-1,1,1,4,4,4-hexafluoro-2-butene and methyl-formiate or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,1,3,3-3-pentafluorobutane; (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) cis-1,1,1,4,4,4-hexafluoro-2-butene and anti-form-1, the azeotropic of 2-Ethylene Dichloride or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) azeotropic of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentane or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) azeotropic of cis-1,1,1,4,4,4-hexafluoro-2-butene and iso-pentane or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) azeotropic of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentamethylene or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and HFC-245fa; (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure provides formation of foam composition, and described formation of foam composition comprises: (a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and Methylal(dimethoxymethane); (b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The disclosure also provides closed-cell polyurethane or the poly-isocyanurate foam of polymers prepared with reacting of suitable polyisocyanate by the formation of foam composition of significant quantity.
The disclosure content also provides the method for the preparation of closed-cell polyurethane or poly-isocyanurate foam of polymers.Described method comprises makes the formation of foam composition of significant quantity react with suitable polyisocyanates.
Detailed Description Of The Invention
Foaming agent composotion (being also called as foam expansion agent or foam intumescent composition) is expected conventionally for single pure component or azeotropic or Azeotrope-like mixtures.For example, in the time that foaming agent composotion is not single pure component or azeotropic or Azeotrope-like mixtures, described composition can change during it is applied to formation of foam process.This composition changes adversely impact to be processed, or in application, causes degradation.Therefore, need to comprise Z-FC-1336mzz by use and prepare urethane/polyisocyanurate foam as azeotropic or the Azeotrope-like mixtures of whipping agent.
Before proposing following embodiment details, first define or illustrate some terms.
So-called " newborn thick time " refers to and mixes beginning with polyisocyanates from active hydrogen-contg compound until foam starts the time period finishing when appearance and mixture color start to change.
So-called " foamed time " refers to and mixes beginning with polyisocyanates from active hydrogen-contg compound until the time period finishing while stopping foaming.
So-called " sticky time " refers to and mixes beginning with polyisocyanates from active hydrogen-contg compound until the time period that foam surface finishes while being no longer clamminess.
So-called " Initial R-value " refer under 75 °F of medial temperatures, at formation of foam and cannot not become stickyly the foam of polymers thermal-insulating value (T.I.V.) (thermal resistance) recording in latter 24 hours.
Z-FC-1336mzz is known compound, and its preparation method has for example been disclosed in U.S. Patent Publication US2008/0269532, accordingly described document is incorporated to way of reference in full.
Present patent application comprises formation of foam composition, and described formation of foam composition comprises (a) azeotropic or Azeotrope-like mixtures containing Z-FC-1336mzz; (b) compound that comprises active hydrogen.
In some embodiments of the present invention, described formation of foam composition comprises: (a) azeotropic of Z-FC-1336mzz and methyl-formiate or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, the azeotropic of use Z-FC-1336mzz and methyl-formiate or Azeotrope-like mixtures are as whipping agent.Whipping agent Z-FC-1336mzz and methyl-formiate form Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add methyl-formiate.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 1 % by weight to 99 % by weight and the methyl-formiate of 99 % by weight to 1 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 50 % by weight to 92 % by weight and the methyl-formiate of 50 % by weight to 8 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 90 % by weight and the methyl-formiate of 10 % by weight.
The azeotropic of Z-FC-1336mzz and methyl-formiate or Azeotrope-like mixtures have been described in the U.S. Patent application 60/926617[FL1369 US PRV submitting on April 27th, 2007] in, accordingly described document is incorporated to way of reference in full.
In some embodiments of the present invention, described formation of foam composition comprises: (a) Azeotrope-like mixtures of Z-FC-1336mzz and 1,1,1,3,3-3-pentafluorobutane; (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, use Z-FC-1336mzz and 1,1,1,3,3-3-pentafluorobutane (HFC-365mfc or CF
3cH
2cF
2cH
3) Azeotrope-like mixtures as whipping agent.Whipping agent Z-FC-1336mzz and HFC-365mfc form Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add HFC-365mfc.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 1 % by weight to 99 % by weight and the HFC-365mfc of 99 % by weight to 1 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 45 % by weight to 95 % by weight and the HFC-365mfc of 55 % by weight to 5 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 80 % by weight and the HFC-365mfc of 20 % by weight.
The Azeotrope-like mixtures of Z-FC-1336mzz and HFC-365mfc has been described in the U.S. Patent application 60/930383[FL1401 US PRV submitting on May 16th, 2007] in, accordingly described document is incorporated to way of reference in full.
In some embodiments of the present invention, described formation of foam composition comprises: (a) Z-FC-1336mzz and anti-form-1, the azeotropic of 2-Ethylene Dichloride or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, use Z-FC-1336mzz and anti-form-1, the azeotropic of 2-Ethylene Dichloride (anti-form-1,2-DCE or trans-ClCH=CHCl) or Azeotrope-like mixtures are as whipping agent.Whipping agent Z-FC-1336mzz and anti-form-1,2-Ethylene Dichloride forms Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add anti-form-1,2-Ethylene Dichloride.In one embodiment, the anti-form-1 of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 66 % by weight to 99 % by weight and 34 % by weight to 1 % by weight, 2-Ethylene Dichloride.In one embodiment, the anti-form-1 of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 68 % by weight to 95 % by weight and 32 % by weight to 5 % by weight, 2-Ethylene Dichloride.In one embodiment, the anti-form-1 of the Z-FC-1336mzz that described azeotropic mixture comprises 74.7 % by weight and 25.3 % by weight, 2-Ethylene Dichloride.In one embodiment, the anti-form-1 of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 68 % by weight and 32 % by weight, 2-Ethylene Dichloride.
Z-FC-1336mzz and anti-form-1, the azeotropic of 2-Ethylene Dichloride or Azeotrope-like mixtures have been described in the U.S. Patent application 60/931960[FL1404 US PRV submitting on May 24th, 2007] in, accordingly described document is incorporated to way of reference in full.
In some embodiments of the present invention, described formation of foam composition comprises: (a) azeotropic of Z-FC-1336mzz and pentane or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, the azeotropic of use Z-FC-1336mzz and pentane or Azeotrope-like mixtures are as whipping agent.Whipping agent Z-FC-1336mzz and pentane form Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add pentane.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 62 % by weight to 78 % by weight and the pentane of 38 % by weight to 22 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 64 % by weight to 76 % by weight and the pentane of 36 % by weight to 24 % by weight.In one embodiment, the Z-FC-1336mzz that described azeotropic mixture comprises 70.2 % by weight and the pentane of 29.8 % by weight.
The azeotropic of Z-FC-1336mzz and pentane or Azeotrope-like mixtures have been described in the U.S. Patent application 60/930467[FL1394 US PRV submitting on May 16th, 2007] in, accordingly described document is incorporated to way of reference in full.
In some embodiments of the present invention, described formation of foam composition comprises: (a) azeotropic of Z-FC-1336mzz and iso-pentane or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, the azeotropic of use Z-FC-1336mzz and iso-pentane or Azeotrope-like mixtures are as whipping agent.Whipping agent Z-FC-1336mzz and iso-pentane form Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add iso-pentane.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 51 % by weight to 70 % by weight and the iso-pentane of 49 % by weight to 30 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 54 % by weight to 67 % by weight and the iso-pentane of 46 % by weight to 33 % by weight.In one embodiment, the Z-FC-1336mzz that described azeotropic mixture comprises 61.4 % by weight and the iso-pentane of 38.6 % by weight.
The azeotropic of Z-FC-1336mzz and iso-pentane or Azeotrope-like mixtures have been described in the U.S. Patent application 60/930445[FL1395 US PRV submitting on May 16th, 2007] in, accordingly described document is incorporated to way of reference in full.
In some embodiments of the present invention, described formation of foam composition comprises: (a) azeotropic of Z-FC-1336mzz and pentamethylene or Azeotrope-like mixtures; (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, the azeotropic of use Z-FC-1336mzz and pentamethylene or Azeotrope-like mixtures are as whipping agent.Whipping agent Z-FC-1336mzz and pentamethylene form Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add pentamethylene.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 75 % by weight to 88 % by weight and the pentamethylene of 25 % by weight to 12 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 77 % by weight to 87 % by weight and the pentamethylene of 23 % by weight to 13 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 85 % by weight and the pentamethylene of 15 % by weight.
The azeotropic of Z-FC-1336mzz and pentamethylene or Azeotrope-like mixtures have been described in the U.S. Patent application 60/999871[FL1445 US PRV submitting on October 22nd, 2007] in, accordingly described document is incorporated to way of reference in full.
In some embodiments of the present invention, described formation of foam composition comprises: (a) Azeotrope-like mixtures of Z-FC-1336mzz and HFC-245fa; (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, use the Azeotrope-like mixtures of Z-FC-1336mzz and HFC-245fa as whipping agent.Whipping agent Z-FC-1336mzz and HFC-245fa form Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add HFC-245fa.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 1 % by weight to 24 % by weight and the HFC-245fa of 99 % by weight to 76 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 3 % by weight to 22 % by weight and the HFC-245fa of 97 % by weight to 78 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 20 % by weight and the HFC-245fa of 80 % by weight.
The Azeotrope-like mixtures of Z-FC-1336mzz and HFC-245fa has been described in the U.S. Patent application 60/931875[FL1405 US PRV submitting on May 24th, 2007] in, accordingly described document is incorporated to way of reference in full.
In some embodiments of the present invention, described formation of foam composition comprises: (a) Azeotrope-like mixtures of Z-FC-1336mzz and Methylal(dimethoxymethane); (b) there is the compound that comprises active hydrogen of the active hydrogen of two or more OH-form.In the disclosure, use the Azeotrope-like mixtures of Z-FC-1336mzz and Methylal(dimethoxymethane) as whipping agent.Whipping agent Z-FC-1336mzz and Methylal(dimethoxymethane) form Azeotrope-like mixtures.Conventionally, before mixing with other component in formation of foam composition, by these mixing.Alternatively, can make one mix with part or all of other component, then sneak into another kind.For example, can make Z-FC-1336mzz first mix with other component in formation of foam composition, then add Methylal(dimethoxymethane).In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 1 % by weight to 99 % by weight and the Methylal(dimethoxymethane) of 99 % by weight to 1 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 67 % by weight to 97 % by weight and the Methylal(dimethoxymethane) of 33 % by weight to 3 % by weight.In one embodiment, the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 85 % by weight and the Methylal(dimethoxymethane) of 15 % by weight.
The Azeotrope-like mixtures of Z-FC-1336mzz and Methylal(dimethoxymethane) has been described in the U.S. Patent application 60/967874[FL1427 US PRV submitting on September 7th, 2007] in, accordingly described document is incorporated to way of reference in full.
As recognized this area, azeotropic or Azeotrope-like mixtures are the mixtures of two or more different componentss, when be liquid form under setting pressure time, described mixture will seethe with excitement at the temperature of substantially constant, described temperature can be higher or lower than the independent boiling temperature of component, and will provide substantially and form identical vapor composition with the liquid of experience boiling.
For the object of this discussion, Azeotrope-like mixtures refers to the composition (i.e. boiling or when evaporation have azeotropic characteristic or without fractionation trend) of performance Azeotrope-like.The composition of the steam therefore, forming during boiling or evaporation is identical or basic identical with primary liquid composition.Therefore, during boiling or evaporation, change if some have occurred liquid composition, the variation that minimum degree maybe can be ignored degree also only occurs.This and non-Azeotrope-like compositions form contrast, and non-Azeotrope-like compositions is that the composition that significance degree changes has occurred liquid composition during boiling or evaporation.
In addition, Azeotrope-like compositions shows almost dew point pressure and the bubble point pressure without pressure reduction.That is to say, under fixed temperature, dew point is pressed and the difference of bubble point pressure is very little value.In the present invention, the difference that dew point is pressed and bubble point is pressed is less than or equal to 3% composition of (based on bubble point pressure) is considered to class azeotropic.
Therefore, the essential characteristic of azeotropic or Azeotrope-like compositions is: under setting pressure, the boiling point of liquid composition is fixed, and the vapor composition of boiling composition top is exactly the composition (, the fractionation of liquid composition component does not occur) of boiling liquid composition substantially.This area also recognizes, in the time making azeotropic or class azeotropic liquid composition experience boiling under different pressures, in Azeotrope compositions, the boiling point of every kind of component and weight percent all can change.Therefore, be characterised in that under specified pressure, have the azeotropic of fixing boiling point or Azeotrope-like compositions can by be present in unique relationship between each component or by the compositing range of these components or in by composition the accurate weight percentage of every kind of component recently define.This area is also recognized, can calculate various Azeotrope compositions (comprising its boiling point under concrete pressure) (referring to as W.Schotte " Ind.Eng.Chem.Process Des.Dev. ",, 19, the 432 to 439 pages in 1980).Can confirm the accuracy of this type of calculating under identical or other temperature and pressure and/or it is revised with the experimental identification of the Azeotrope compositions that relates to same composition.
Active hydrogen-contg compound of the present invention can comprise the compound with two or more groups that comprise active hydrogen atom that react with isocyanate groups, discloses 4,394 such as United States Patent (USP), those that describe in 491; Described document is incorporated to way of reference.The example of this compounds has at least two hydroxyl per molecules, and more particularly comprises polyvalent alcohol, such as polyethers or polyester polyol.The example of this type of polyvalent alcohol is that equivalent is approximately 50 to approximately 700, is generally approximately 70 to approximately 300, is more typically approximately 90 to approximately 270 and with at least 2 hydroxyls, those of general 3 to 8 these type of groups.
The example of suitable polyvalent alcohol comprises polyester polyol, such as aromatic polyester polyols, those that are for example undertaken prepared by transesterify by polyethylene terephthalate scrap (PET) and glycol such as glycol ether, or reacted those that prepare with glycol by Tetra hydro Phthalic anhydride.Gained polyester polyol also can form the expansion polyester polyol that comprises extra inside alkylidene group oxygen base with ethene-and/or propylene oxide-react.
The example of suitable polyvalent alcohol also comprises polyether glycol, such as polyethylene oxide, poly(propylene oxide), have mixing polyethylene oxide-propylene oxide of terminal hydroxyl etc.Other suitable polyvalent alcohol can be prepared with reacting of initiator by oxyethane and/or propylene oxide, described initiator has 2 to 16, the hydroxyl existing in the polyols such as general 3 to 8 such as glycerine, tetramethylolmethane and carbohydrate such as sorbyl alcohol, glucose, sucrose.Suitable polyether glycol also comprises the polyvalent alcohol based on fatty amine or aromatic amine.
The invention still further relates to the method for being reacted to prepare closed-cell polyurethane or poly-isocyanurate foam of polymers by significant quantity formation of foam composition with suitable polyisocyanate.
Conventionally,, before reacting with suitable polyisocyanate, make the compound that comprises active hydrogen mentioned above and other optional additive mix to form formation of foam composition with whipping agent.This type of formation of foam composition is called as isocyanate reaction pre-composition or B end composition conventionally in this area.Formation of foam composition of the present invention can be to those skilled in the art easily any mode prepare, comprise every kind of component of simple weighing aequum, in suitable container, under suitable temperature and pressure, they are mixed afterwards.
In the time of the foam of preparation based on polyisocyanates, the ratio of polyisocyanates reactant and active hydrogen-contg compound is selected such that the ratio (being foam index) of isocyanate groups equivalent and active hydrogen group equivalent is approximately 0.9 to approximately 10 conventionally, and is in most of the cases approximately 1 to approximately 4.
Although can use in the methods of the invention any suitable polyisocyanates, the suitable polyisocyanate example that can be used for the foam of preparation based on polyisocyanates comprises at least one aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanates etc.The representative member of these compounds comprises vulcabond, such as m-benzene diisocyanate or PPDI, Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, hexanaphthene-1, 6-vulcabond, tetramethylene-1, 4-vulcabond, hexanaphthene-1, 4-vulcabond, methylcyclohexane diisocyanate (and isomer), naphthalene-1, 5-vulcabond, 1-aminomethyl phenyl-2, 4-phenyl diisocyanate, ditan-4, 4-vulcabond, ditan-2, 4-vulcabond, 4, 4-biphenyl diisocyanate and 3, 3-dimethoxy-4 ', 4-biphenyl diisocyanate and 3, 3-dimethyl diphenyl propane-4, 4-vulcabond, triisocyanate, such as Toluene-2,4-diisocyanate, 4,6-triisocyanate and polyisocyanates be such as 4,4-dimethyl diphenylmethane-2,2,5,5-tetraisocyanate and various poly methylene poly phenyl poly isocyanate, their mixture etc.
In practice of the present invention, also can use rough polyisocyanates, such as by the rough tolylene diisocyanate that the mixture phosgenation that comprises tolylene diamine is obtained, or by the rough diphenylmethanediisocyanate that rough diphenylmethane diamine phosgenation is obtained.The specific examples of this compounds comprises the polyphenyl polyisocyanate of methylene-bridged, and this is the ability of their cross-linked polyurethanes due to.
In foam in preparation based on polyisocyanates, conventionally expect to use trace mineral supplement.Wherein these additives comprise following one or more members well known in the art: catalyzer, tensio-active agent, fire retardant, sanitas, tinting material, antioxidant, toughener, filler, static inhibitor etc.
According to described composition, can use tensio-active agent to stablize foamed reaction mixture when curing.This type of tensio-active agent generally comprises liquid or solid organosilicone compounds.The consumption of described tensio-active agent should be enough to stablize foamed reaction mixture, prevents from collapsing, and prevents from forming inhomogeneous macroporous cavity.In one embodiment of the invention, use by the tensio-active agent of all foaming ingredients (being whipping agent+active hydrogen-contg compound+polyisocyanates+additive) gross weight approximately 0.1% to approximately 5%.In another embodiment of the invention, use by the tensio-active agent of all foaming ingredient gross weights approximately 1.5% to approximately 3%.
Also can use one or more for the active hydrogen-contg compound catalyzer that for example polyvalent alcohol reacts with polyisocyanates.Although can use any suitable catalysts for polyurethanes, concrete catalyzer comprises tertiary amine compound and organometallic compound.This type of exemplary catalyzer is disclosed in for example United States Patent (USP) and discloses 5,164, and in 419, its disclosure is incorporated herein by reference.For example, also can optionally use the catalyzer for polyisocyanates trimerization reaction herein, such as alkali metal alcoholates, alkali metal carboxylate or quaternary ammonium compound.Use this type of catalyzer with the amount that can mensuration degree increases polyisocyanates speed of reaction.The typical amount of catalyzer counts approximately 0.1% to approximately 5% by all foaming ingredient gross weights.
In the inventive method of the foam for the preparation of based on polyisocyanates, make active hydrogen-contg compound (for example polyvalent alcohol), polyisocyanates and the contact of other component, fully mix, and make its expansion and be solidified into spumescence polymkeric substance.Mixing equipment is not critical, and can use stirring-head and the spraying equipment of various general types.Conventional equipment refers to conventional equipment, utensil and method for the preparation of the foam based on isocyanic ester, wherein uses the conventional foam foaming agent based on isocyanic ester, such as trichlorofluoromethane (CCl3F, CFC-11).This type of conventional equipment is discussed in: the people's such as H.Boden Polyurethane Handbook the 4th chapter (being edited HanserPublishers, New York, 1985 years by G.Oertel); People's exercise questions such as the H.Grunbauer that Proceed ings of the SPI 34th Annual Technical/Marketing Conference on October 21st, 1992 to October 24 (New Orleans, Louisiana) announces in Polyurethanes 92 are the paper of " Fine Celled CFC-Free Rigid Foam-New Machinery withLow Boiling whipping agent s "; And people's exercise question such as M.Taverna be " Solubleor Insoluble Alternative whipping agent s? Processing Technologies forBoth Alternatives; Presented by the Equipment Manufacturer " paper in (on September 24th, 1991 is to 26Proceedings of the SPI/ISOPA (Acropolis, Nice, France) in Polyurethanes World Congress 1991, announce).These disclosures are incorporated to way of reference.
In one embodiment of the invention, make polyisocyanates and the pre-composition of preparing some raw material containing active hydrogen component before reacting.For example, conventionally usefully, except polyisocyanates, by polyvalent alcohol, whipping agent, tensio-active agent, catalyzer and other foaming ingredient blend, then make this blend contact with polyisocyanates.Alternatively, all foaming ingredients are introduced separately in mixing region, in described mixing region, polyisocyanates are contacted with polyvalent alcohol.Also can make all or part polyvalent alcohol and polyisocyanates pre-reaction to form prepolymer.
The compositions and methods of the invention are suitable for preparing all types of expanded polyurethane foams, comprise for example from cutification, RIM and flexible foam, in spraying type thermal insulation, be used as specifically on-the-spot mould and water equipment foam, or be used as the rigidity closed cell polymeric foam of rigid insulation boards material and layered product.
The invention still further relates to the closed-cell polyurethane or the poly-isocyanurate foam of polymers that are reacted preparation by significant quantity formation of foam composition of the present disclosure with suitable polyisocyanate.
Embodiment
Disclosure of the present invention further definition in the following embodiments.Although should be appreciated that these embodiment have illustrated preferred embodiment, be only to provide in the mode of illustration.By above discussion and these embodiment, those skilled in the art can determine preferred feature, and is not deviating under the prerequisite of the spirit and scope of the present invention, can carry out variations and modifications so that it is applicable to various uses and condition.
Polyvalent alcohol is the aromatic-polyether polyvalent alcohol that originates in tolylene diamine (o-TDA) (VORANOL 391) of buying from Dow Chemicals Inc. (Midland, MI, 49641-1206).Polyvalent alcohol has the viscosity of 4740 centipoises at 25 DEG C.Hydroxy radical content in polyvalent alcohol is equal to 391mg KOH/g polyvalent alcohol.
Silicon class tensio-active agent is from Momentive Performance Materials (187Danbury Road, Wilton, CT, 06897USA) the 70% polyalkylene oxide methylsiloxane of buying and the mixture of 30% polyalkylene oxide (Niax Silicone L-5440).
Amine catalyst (Polycat 8) is the N buying from Air Products Inc. (7201 HamiltonBlvd, Allentown, PA, 18195), N-dimethylcyclohexylamine.
Promotor (Curithane 52) is the 2-methyl (N-methylamino b-sodium acetate nonylphenol) of buying from Air Products Inc. (7201 HamiltonBlvd, Allentown, PA, 18195).
Polymethylene multi-phenenyl isocyanate (PAPI 27) is from Dow Chemicals, and Inc. (Midland, MI, 49641-1206) buys.
Under 75 °F of medial temperatures, measure Initial R-value with LaserComp FOX 304 thermal conductivity meters.R value unit is ft
2-hr-°F/BTU-in.
embodiment 1
the polyurethane foam of being prepared by Z-FC-1336mzz and methyl-formiate Azeotrope-like mixtures
By whipping agent Z-FC-1336mzz and methyl-formiate premix to form Azeotrope-like mixtures, the methyl-formiate of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 90 % by weight and 10 % by weight.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (Z-FC-1336mzz of the methyl-formiate of 10 % by weight and 90 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 1 and 2.
table 1: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (methyl-formiates of the Z-FC-1336mzz of 90 % by weight and 10 % by weight) | 25.1 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 2: polyurethane foam characteristic
| Foam index | 1.22 |
| Breast thick time (second) | 8 |
| Foamed time (second) | 90 |
| The not sticky time (second) | 100 |
| Foam density (pound/cubic feet) | 2.3 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 7.3 |
embodiment 2
the polyurethane foam of being prepared by Z-FC-1336mzz and HFC-365mfc Azeotrope-like mixtures
By whipping agent Z-FC-1336mzz and HFC-365mfc premix to form Azeotrope-like mixtures, the HFC-365mfc of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 80 % by weight and 20 % by weight.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (Z-FC-1336mzz of the HFC-365mfc of 20 % by weight and 80 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 3 and 4.
table 3: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (HFC-365mfc of the Z-FC-1336mzz of 80 % by weight and 20 % by weight) | 28.8 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 4: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 8 |
| Foamed time (second) | 90 |
| The not sticky time (second) | 100 |
| Foam density (pound/cubic feet) | 2.2 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 7.4 |
embodiment 3
by Z-FC-1336mzz and anti-form-1, polyurethane foam prepared by 2-Ethylene Dichloride azeotropic mixture
By whipping agent Z-FC-1336mzz and anti-form-1,2-Ethylene Dichloride premix is to form azeotropic mixture, the anti-form-1 of the Z-FC-1336mzz that described azeotropic mixture comprises 74.7 % by weight and 25.3 % by weight, 2-Ethylene Dichloride.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (anti-form-1 of 25.3 % by weight, the Z-FC-1336mzz of 2-Ethylene Dichloride and 74.7 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 5 and 6.
table 5: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (anti-form-1 of the Z-FC-1336mzz of 74.7 % by weight and 25.3 % by weight, 2-Ethylene Dichloride) | 25.1 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 6: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 11 |
| Foamed time (second) | 90 |
| The not sticky time (second) | 100 |
| Foam density (pound/cubic feet) | 2.1 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 7.1 |
embodiment 4
by Z-FC-1336mzz and anti-form-1, polyurethane foam prepared by 2-Ethylene Dichloride Azeotrope-like mixtures
foam
By whipping agent Z-FC-1336mzz and anti-form-1,2-Ethylene Dichloride premix is to form Azeotrope-like mixtures, the anti-form-1 of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 68 % by weight and 32 % by weight, 2-Ethylene Dichloride.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (anti-form-1 of 32 % by weight, the Z-FC-1336mzz of 2-Ethylene Dichloride and 68 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 7 and 8.
table 7: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (anti-form-1 of the Z-FC-1336mzz of 68 % by weight and 32 % by weight, 2-Ethylene Dichloride) | 24.1 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 8: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 9 |
| Foamed time (second) | 88 |
| The not sticky time (second) | 93 |
| Foam density (pound/cubic feet) | 2.3 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 7.2 |
embodiment 5
the polyurethane foam of being prepared by Z-FC-1336mzz and pentane azeotropic mixture
By whipping agent Z-FC-1336mzz and pentane premix to form azeotropic mixture, the pentane of the Z-FC-1336mzz that described azeotropic mixture comprises 70.2 % by weight and 29.8 % by weight.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (Z-FC-1336mzz of the pentane of 29.8 % by weight and 70.2 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 9 and 10.
table 9: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (pentanes of the Z-FC-1336mzz of 70.2 % by weight and 29.8 % by weight) | 21.4 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 10: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 9 |
| Foamed time (second) | 90 |
| The not sticky time (second) | 100 |
| Foam density (pound/cubic feet) | 2.3 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 6.9 |
embodiment 6
the polyurethane foam of being prepared by Z-FC-1336mzz and iso-pentane azeotropic mixture
By whipping agent Z-FC-1336mzz and pentane premix to form azeotropic mixture, the iso-pentane of the Z-FC-1336mzz that described azeotropic mixture comprises 61.4 % by weight and 38.6 % by weight.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (Z-FC-1336mzz of the iso-pentane of 38.6 % by weight and 61.4 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 11 and 12.
table 11: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (iso-pentane of the Z-FC-1336mzz of 61.4 % by weight and 38.6 % by weight) | 19.7 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 12: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 7 |
| Foamed time (second) | 80 |
| The not sticky time (second) | 90 |
| Foam density (pound/cubic feet) | 1.8 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 6.5 |
embodiment 7
the polyurethane foam of being prepared by Z-FC-1336mzz and cyclopentanes azeotropic mixture
By whipping agent Z-FC-1336mzz and pentamethylene premix to form Azeotrope-like mixtures, the pentamethylene of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 85 % by weight and 15 % by weight.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (Z-FC-1336mzz of the pentamethylene of 15 % by weight and 85 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 13 and 14.
table 13: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (pentamethylene of the Z-FC-1336mzz of 85 % by weight and 15 % by weight) | 24.5 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 14: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 10 |
| Foamed time (second) | 85 |
| The not sticky time (second) | 95 |
| Foam density (pound/cubic feet) | 2.3 |
| Just R value (ft 2-hr-°F/BTU-in) | 7.3 |
embodiment 8
the polyurethane foam of being prepared by Z-FC-1336mzz and HFC-245fa Azeotrope-like mixtures
By whipping agent Z-FC-1336mzz and HFC-245fa premix to form Azeotrope-like mixtures, the HFC-245fa of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 20 % by weight and 80 % by weight.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (Z-FC-1336mzz of the HFC-245fa of 80 % by weight and 20 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 15 and 16.
table 15: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (HFC-245fa of the Z-FC-1336mzz of 20 % by weight and 80 % by weight) | 25.0 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 16: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 7 |
| Foamed time (second) | 90 |
| The not sticky time (second) | 90 |
| Foam density (pound/cubic feet) | 2.4 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 7.1 |
embodiment 9
the polyurethane foam of being prepared by Z-FC-1336mzz and Methylal(dimethoxymethane) Azeotrope-like mixtures
By whipping agent Z-FC-1336mzz and Methylal(dimethoxymethane) premix to form Azeotrope-like mixtures, the Methylal(dimethoxymethane) of the Z-FC-1336mzz that described Azeotrope-like mixtures comprises 85 % by weight and 15 % by weight.
Manually, by polyvalent alcohol, tensio-active agent, catalyzer, water and whipping agent (Z-FC-1336mzz of the Methylal(dimethoxymethane) of 15 % by weight and 85 % by weight) premix, then mix with polyisocyanates.Gained mixture is poured into 8 " × 8 " × 2.5 " in carton with form polyurethane foam.The formula of foam and performance are shown in following table 17 and 18.
table 17: polyurethane formulation
| Component | Weight part |
| Polyvalent alcohol | 100 |
| Silicon class tensio-active agent | 2.0 |
| Amine catalyst | 1.5 |
| Promotor | 0.5 |
| Water | 1.0 |
| Whipping agent (Methylal(dimethoxymethane) of the Z-FC-1336mzz of 85 % by weight and 15 % by weight) | 25.1 |
| Polymethylene multi-phenenyl isocyanate | 132 |
table 18: polyurethane foam characteristic
| Foam index | 1.2 |
| Breast thick time (second) | 7 |
| Foamed time (second) | 85 |
| The not sticky time (second) | 105 |
| Foam density (pound/cubic feet) | 2.0 |
| Initial R-value (ft 2-hr-°F/BTU-in) | 6.8 |
Claims (17)
1. formation of foam composition, described formation of foam composition comprises:
(a) azeotropic mixture of cis-1,1,1,4,4,4-hexafluoro-2-butene and methyl-formiate; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
2. formation of foam composition, described formation of foam composition comprises:
(a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and methyl-formiate; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
3. formation of foam composition, described formation of foam composition comprises:
(a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,1,3,3-3-pentafluorobutane; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
4. formation of foam composition, described formation of foam composition comprises:
(a) cis-1,1,1,4,4,4-hexafluoro-2-butene and anti-form-1, the azeotropic mixture of 2-Ethylene Dichloride; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
5. formation of foam composition, described formation of foam composition comprises:
(a) anti-form-1 of the cis-1,1,1,4,4,4-hexafluoro-2-butene of 66 % by weight to 99 % by weight and 34 % by weight to 1 % by weight, the Azeotrope-like mixtures of 2-Ethylene Dichloride; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
6. formation of foam composition, described formation of foam composition comprises:
(a) azeotropic mixture of the pentane of the cis-1,1,1,4,4,4-hexafluoro-2-butene of 70.2 % by weight and 29.8 % by weight; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
7. formation of foam composition, described formation of foam composition comprises:
(a) Azeotrope-like mixtures of the pentane of the cis-1,1,1,4,4,4-hexafluoro-2-butene of 62 % by weight to 78 % by weight and 38 % by weight to 22 % by weight; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
8. formation of foam composition, described formation of foam composition comprises:
(a) azeotropic mixture of the iso-pentane of the cis-1,1,1,4,4,4-hexafluoro-2-butene of 61.4 % by weight and 38.6 % by weight; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
9. formation of foam composition, described formation of foam composition comprises:
(a) Azeotrope-like mixtures of the iso-pentane of the cis-1,1,1,4,4,4-hexafluoro-2-butene of 51 % by weight to 70 % by weight and 49 % by weight to 30 % by weight; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
10. formation of foam composition, described formation of foam composition comprises:
(a) azeotropic mixture of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentamethylene; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
11. formation of foam compositions, described formation of foam composition comprises:
(a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and pentamethylene; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
12. formation of foam compositions, described formation of foam composition comprises:
(a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and 1,1,1,3,3-pentafluoropropane; With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
13. formation of foam compositions, described formation of foam composition comprises:
(a) Azeotrope-like mixtures of cis-1,1,1,4,4,4-hexafluoro-2-butene and Methylal(dimethoxymethane); With
(b) there is the compound that comprises active hydrogen of two or more active hydrogens.
The formation of foam composition of 14. aforementioned any one claims, the wherein said compound that comprises active hydrogen is polyether glycol.
15. closed-cell polyurethanes or poly-isocyanurate foam of polymers, described foam is prepared with suitable reacting of polyisocyanates by the formation of foam composition of the aforementioned any one claim of significant quantity.
The closed-cell polyurethane of 16. claims 15 or poly-isocyanurate foam of polymers, wherein said foam of polymers has the 6.0ft of being greater than
2the Initial R-value of-hr-°F/BTU-in.
17. prepare the method for closed-cell polyurethane or poly-isocyanurate foam of polymers, and described method comprises that the formation of foam composition of any one in the claim 1 to 14 that makes significant quantity reacts with suitable polyisocyanates.
Applications Claiming Priority (25)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1508607P | 2007-12-19 | 2007-12-19 | |
| US1502707P | 2007-12-19 | 2007-12-19 | |
| US1509207P | 2007-12-19 | 2007-12-19 | |
| US1506107P | 2007-12-19 | 2007-12-19 | |
| US1508907P | 2007-12-19 | 2007-12-19 | |
| US61/015089 | 2007-12-19 | ||
| US61/015092 | 2007-12-19 | ||
| US61/015,089 | 2007-12-19 | ||
| US61/015086 | 2007-12-19 | ||
| US61/015,092 | 2007-12-19 | ||
| US61/015,027 | 2007-12-19 | ||
| US61/015027 | 2007-12-19 | ||
| US61/015061 | 2007-12-19 | ||
| US61/015,061 | 2007-12-19 | ||
| US61/015,086 | 2007-12-19 | ||
| US1522107P | 2007-12-20 | 2007-12-20 | |
| US1521407P | 2007-12-20 | 2007-12-20 | |
| US1521807P | 2007-12-20 | 2007-12-20 | |
| US61/015,221 | 2007-12-20 | ||
| US61/015,218 | 2007-12-20 | ||
| US61/015218 | 2007-12-20 | ||
| US61/015214 | 2007-12-20 | ||
| US61/015221 | 2007-12-20 | ||
| US61/015,214 | 2007-12-20 | ||
| PCT/US2008/087227 WO2009085857A2 (en) | 2007-12-19 | 2008-12-17 | Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing z-1,1,1,4,4,4-hexafluoro-2-butene and their uses in the preparation of polyisocyanate-based foams |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101903435A CN101903435A (en) | 2010-12-01 |
| CN101903435B true CN101903435B (en) | 2014-07-23 |
Family
ID=40565188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880121602.5A Active CN101903435B (en) | 2007-12-19 | 2008-12-17 | Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing z-1,1,1,4,4,4-hexafluoro-2-butene and their uses in the preparation of polyisocyanate-based foams |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US8658708B2 (en) |
| EP (5) | EP2567991B1 (en) |
| JP (2) | JP5703027B2 (en) |
| KR (3) | KR101590653B1 (en) |
| CN (1) | CN101903435B (en) |
| AR (1) | AR070677A1 (en) |
| AU (1) | AU2008343200A1 (en) |
| BR (1) | BRPI0819469B1 (en) |
| CA (4) | CA2941024C (en) |
| ES (5) | ES2548184T3 (en) |
| WO (1) | WO2009085857A2 (en) |
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| US20050269549A1 (en) * | 2004-06-02 | 2005-12-08 | Jinhuang Wu | Polyol premixes incorporating trans-1, 2-dichloroethylene |
| JP2008546634A (en) | 2005-03-16 | 2008-12-25 | ハネウェル・インターナショナル・インコーポレーテッド | Pharmaceutical delivery formulations, devices and methods |
| US20070077488A1 (en) | 2005-10-04 | 2007-04-05 | Kaimin Chen | Power capability of a cathode |
| US7708903B2 (en) | 2005-11-01 | 2010-05-04 | E.I. Du Pont De Nemours And Company | Compositions comprising fluoroolefins and uses thereof |
| US8287752B2 (en) | 2005-11-01 | 2012-10-16 | E I Du Pont De Nemours And Company | Fire extinguishing and fire suppression compositions comprising unsaturated fluorocarbons |
| US20070100010A1 (en) | 2005-11-01 | 2007-05-03 | Creazzo Joseph A | Blowing agents for forming foam comprising unsaturated fluorocarbons |
| US20070098646A1 (en) | 2005-11-01 | 2007-05-03 | Nappa Mario J | Aerosol propellants comprising unsaturated fluorocarbons |
| MY151990A (en) | 2005-11-01 | 2014-07-31 | Du Pont | Solvent compositions comprising unsaturated fluorinated hydrocarbons |
| US7498296B2 (en) | 2006-02-28 | 2009-03-03 | E. I. Dupont De Nemours And Company | Azeotropic compositions comprising fluorinated compounds for cleaning applications |
| RU2006139128A (en) | 2006-11-07 | 2008-05-20 | Е.И.Дюпон де Немур энд Компани (US) | METHOD FOR PRODUCING FLORATED OLEFINS |
| US8618339B2 (en) | 2007-04-26 | 2013-12-31 | E I Du Pont De Nemours And Company | High selectivity process to make dihydrofluoroalkenes |
| WO2008134061A2 (en) * | 2007-04-27 | 2008-11-06 | E. I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene |
| BR122018074413B1 (en) | 2007-06-12 | 2019-03-19 | E. I. Du Pont De Nemours And Company | COMPOSITION AND PROCESS TO PRODUCE COOLING |
| CA2693203A1 (en) | 2007-07-20 | 2009-01-29 | E.I. Du Pont De Nemours And Company | Compositions and use of trans-1,1,1,4,4,4-hexafluoro-2-butene foam-forming composition in the preparation of polyisocyanate-based foams |
| CA2688087C (en) | 2007-07-20 | 2014-09-09 | E. I. Du Pont De Nemours And Company | Compositions and use of cis-1,1,1,4,4,4-hexafluoro-2-butene foam-forming composition in the preparation of polyisocyanate-based foams |
| BRPI0815462A2 (en) | 2007-09-06 | 2015-02-18 | Du Pont | "COMPOSITION, PROCESSES FOR PREPARATION OF A THERMOPLASTIC OR THERMO-RETRACTABLE FOAM, REFRIGERATION PRODUCTION, MANUFACTURE OF AN AEROSOL PRODUCT, FIRE EXTINCTION OR EXPRESSION" |
| WO2009073487A1 (en) | 2007-11-29 | 2009-06-11 | E. I. Du Pont De Nemours And Company | Compositions and use of cis-1,1,1,4,4,4-hexafluoro-2-butene foam-forming composition in the preparation of polyisocyanate-based foams |
| CA2941024C (en) * | 2007-12-19 | 2018-12-04 | E. I. Du Pont De Nemours And Company | Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing z-1,1,1,4,4,4-hexafluoro-2-butene and their uses in the preparation of polyisocyanate-based foams |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5578137A (en) * | 1993-08-31 | 1996-11-26 | E. I. Du Pont De Nemours And Company | Azeotropic or azeotrope-like compositions including 1,1,1,2,3,4,4,5,5,5-decafluoropentane |
| WO2003068838A1 (en) * | 2002-02-14 | 2003-08-21 | Vulcan Chemicals | Isopropyl chloride with hydrofluorocarbon or hydrofluorether as foam blowing agents |
| WO2006130406A2 (en) * | 2005-05-27 | 2006-12-07 | E. I. Du Pont De Nemours And Company | Compositions comprising 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene |
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| Title |
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| JP特开平5-179043A 1993.07.20 |
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